N-halotrichloroacetamidines



ti -1B7 FIP8309 3,428,681 N-HALOTRICHLOROACETAMIDINES Perry R. Kippur .and Randal E. Bailey, Orange, -Conn.,

assignors, by mesne assignments, to The Ansul Comnited States Patent 3,428,681 Patented Feb. 18, 1969 hexylamine, aniline, ethoxyphenylamine, tolylamine, xylylamine, naphthylamine, benzylamine, piperidylamine and morpholylamine. Suitable secondary amines include dimethylamine, diethylamine, methylethylamine, dibutyl- 5 amine, diphen'ylamine and dinaphthylarnine. 1R3? bi awiig ir i fiii s ezf f l m Ser. No. 576,539 While any of the previously-described trichloroacet- 260 564 3 (jla ms amidines represented by the Formula II can be employed Int. Cl. C07c 129/08; A61k 27/00 in the preparation of the compounds of this invention, preferred embodiments utilize those trichloroacetamidines This invention relates to N-halotrichloroacetamidines h i ach R is independently selected from the group having the f llowing general f r u a! consisting of hydrogen; alkyl having from 1 to 8 carbon NX atoms, i.e., methyl, amyl, octyl and the like; aryl having C1CC R from 6 to 10 carbon atoms, i.e., phenyl, xylyl, tolyl,

3 napthyl, etc.; and benzyl.

N The halogenation of the trichloroacetamidine II is conveniently carried out in the presence of an inert solvent. I Illustrative of the suitable solvents are the chlorinated wherein X is iodine, chlorine or bromine and each R is zggli g igzgi?igf zgig gt g i i g z fi independently Selected from the group consisting of While the reaction can be carried out over atemperadrogen, alkyl, :aryl, cycloalkyl and heterocychc. tum range from about to 400 C a temperature Various substituted acetamidines have been prevlously between a boutoo and C is preferab'iy em loyed In prepared and described in the literature. For example, the the preferred process embmiiments a by d r 0 g; n haiide Preparation of Nichloroacetamidine by the treatment acceptor such as an alkali metal hydroxide or a tertiary eold aeetaelidine hydrochloride with hypeehlonte amine is added to the trichloroacetamidine medium prior has been dlselesed by eee'ldeler et m e to the chlorination. However, satisfactory yields are ob- 400T3 5 H e 'eompeund 1S F tained in the absence of such a material. After completion eempesmg 9. iummg red m elesed eentamer P of the reaction, the desired N-halotrichloroacetamidine I ambient l and exPlodmg when heated rapldly is isolated from the reaction mixture by conventional as dlseussed m the abeve'elted reference .Patent techniques such as filtration centrifuging and the like 671'785 describes the reaeeep of trlchlmalciwmmle The N-lialotrichloroacetamidines of this invention have ammoma to P f e a Substl' a Wide variety of useful applications. They are valuable tuted acelamllme havmg clllorme atoms bound to a P bleaches and disinfectants, liberating halogen in aqueous atom Thls eompe'und 1S unstable deeempesmg media. For example, they are effective bleaches for many ragldly upon exposure to hght at room temperature textiles, including cotton and synthetic fabrics and are and decomposing gradually in the absence of llght. also useful as swimming pool germicides i Now it has been found that a series of N-h'alotrichloropounded with extenders abrasives and i like these acetamldmes y q the I can be convemelltly N-halotrichloroacetamidihes are effective scouring hgents. prepared by selective halogenation of the corresponding These compounds are also useful agricultural chemif l q il e f The no'vel eompounds 9 40 cals, having particularly effective fungicidal herbicidal this lnvention are umque in that they contain both availand algaecidal properties. They are generallymixed with able halogen d chlol'me bound a atom e various adjuvants in these applications, and low conceny lendeflng fi 11$ ef111 for a Wlde val'lety P trations of the compounds are extremely effective. For ext ons. Furthermiore, in contrast to the prevlously-menample, it has been found that these compounds are effectloned substituted acetamrdmes, they are surprislngly s ative both as soil and foliar fungicides against a wide ble, and thus aresmt-abIe in ap lications where pr g variety of plant pathogenic fungi. Thus, a gel containing Storage under val'ylng cnd1t1QI1S1 fi f 100 p.p.m. of N,2,2,Z-tetrachloroacetamidine was essen- The CPmPOIIHdS I am p q 1n hlgh Y and P tially completely eifective in preventing germination of lent purity by halogenatmg trichloroacetamidines 1n ac- Rhizoctonia solani spores, a soipbome fungus harm- Cordance w the following equation wherein R and X 0 ful to a wide variety of economic crops, such as cotton, are as p y descnbedvegetables, potatoes, turf grass and the like.

NH The N-halotrichloroacetamidines I are also effective CIQCC R herbicides, both in preemergence and postemergence applications. Thus, when applied to the soil in preemergence 5 applications and to the foilage in postemergence appli- R cations, N',2,2,Z-tetrachloroacetamidine killed 95 percent 11 of the emerged broadleaf weeds, i.e., mustard and pig- The trichloroacfitamidines H are readily provided by weed, and grasses i.e., ryegrass and crabgrass, and effected reacting trichloroacetonitrile with ammonia or a primary 80 percent preemergence weed control or secondary amine in accordance with known tech-' The algaeeldal effeetlvenese of these compounds h niques. Thus, the treatment of trichloroacetonitrile with 2 5 g g ;3 3 233253 ge i gg ifi g g eg fieggzgg 2222: 555; i e zg s g z fg gg f fii i gg amidine was effective as an aquatic herbicide in inhibiting 771-4 (1958) describe the Preparation of substituted tri- -f ii i g g g gi fgg Chloreua Scenedesmus Pherchloroacetamidines II by the reaction of trichloroacetoni- 011 n c exam will servet nustrat th e trfle with a wide variety of primary and secondary amines ration of an l I-haloti ishloroacetam tiine in acczi i ar i e including aliphatic, heterocyclic, cycloalkyl and aromatic with the ractice of this invention amines. Illustrative primary amines which have been used p in the preparation of compounds II are methylamine, EXAMPLE ethylamine, n-propylamine, isopropylamine, n-butylamine, n-amylamine, n-octylamine, stearylamine, cyclo- In accordance with the procedure described in German Patent 671,785, trichloroacetamidine was prepared in a 5 liter reaction flask by reacting trichloroacetonitrile (578 grams) with ammonia (539 grams).

Methylene dichloride (2,000 grams) was added to the reaction flask at room temperature and the mixture stirred to dissolve the trichloroacetamidine. A solution of 162 grams of sodium hydroxide in 1460 ml. of water was added to the trichloroacetamidine solution and the reaction flask cooled with tap water while stirring the heterogeneous reaction mixture vigorously. Whenthe temperature had fallen to 13 C., the addition of chlorine was initiated. Over a period of one hour, 180 grams of chlorine were added and the reaction mixture separated into two liquid phases. The phases were separated and substantially all the methylene dichloride stripped at 25 C. under water aspirator vacuum in a 2 liter 3-neck flask equipped with an agitator. The resulting slurry was centrifuged to provide 591 grams (76% yield) of a dry cake melting at 48-50 C. The product was purified by distillation at 66.0 C./.05 mm. Hg. The following analytical data revealed that N',2, 2,Z-tetrachloroacetamidine had been obtained.

Analysis calculated for C H N Cl C, 12.25; H, 1.05; N, 14.3; C1, 72.4. Found: C, 12.57; H, 1.2; N, 14.0; C1, 72.0.

Mass spectral analysis of .a sample of the product showed the presence of a molecular ion at m/e 194, corresponding to the molecular weight of N,2,2,2-tetrachloroacetarnidine.

Infrared analysis showed a doublet in the NH stretching region. A strong absorbance at 1,550 emf shifted down to 1,155 cm? upondeuteration of the product, indicating the presence of an NH group.

Nuclear magnetic resonance confirmed the structure of the product.

What is claimed is:

1. A compound having the formula:

ClaCC References Cited Goerdeler et al., Berichte, vol. 86, 400-3 (1953). Robin, Comptes Rendus (Academic Des Sciences), vol. 177, pp. 13046 (1923).

CHARLES B. PARKER, Primary Examiner.

L. C. MARUZO, Assistant Examiner.

US. Cl. X.R.

424-326; 260-290, 247.5; 7167, 88, 94, 121; s 1o7; s1 293; 252 

1. A COMPOUND HAVING THE FORMULA: 